Azo dyes containing fluorinated carboxylic or sulphonic ester groups on the diazo moiety

ABSTRACT

Disclosed are novel azo dyes of the structure 
     
         X--N═N--C&#39; 
    
     wherein X represents the diazonium component comprising phenyl or a heterocyclic group commonly used in azo dyes and which is substituted by one or more fluorinated carboxylic or sulphonic ester groups. Additionally, X may be substituted by any of the groups commonly used in diazonium components such as nitro, cyano, halogen and the like. C&#39; represents an aniline, tetrahydroquinoline or benzomorpholine coupler of the type commonly used in azo dyes. The dyes can be used in both the dyeing and heat transfer printing of textiles, are surprisingly bathochromic in shade, exhibit a good balance of properties such as light, crock, wash, and gas fastness, leveling, pH stability, and dyeability, and have unexpected thermal and hydrolytic stability as compared for example, to the hydrogen analogues. The dyes have particular utility on polyester fibers especially as regards lightfastness.

This invention concerns novel azo dyes of the structure

    X--N═N--C'

wherein X represents a diazonium component selected from phenyl,thienyl, thiazolyl, diazolyl, thiadiazolyl (1,2,4- and 1,3,4-),benzothiazolyl, isothiazolyl, and benzisothiazolyl, all of which aresubstituted by up to two fluorinated carboxylic or sulphonic estergroups, and which may be substituted further with commonly employedsubstituents such as nitro, cyano, halogen, alkoxy, and the like. Thefluorinated ester group is represented by the structure --Z--O--Rwherein Z can be either --CO-- or --SO₂ -- and R represents afluoroaliphatic radical containing from one to eighteen carbon atoms,straight chain, branched chain or alicyclic, and which can be partly orcompletely fluorinated. C' represents an aniline, tetrahydroquinoline orbenzomorpholine coupler of the type commonly used in azo dyes.

The dyes of the present invention can be used for both dyeing and heattransfer printing of textiles in shades from yellow to blue. Thefluorinated ester group in the diazonium component is introduced byreaction of a carboxylic or sulphonic acid or acid chloride with afluorinated alcohol in the presence of pyridine. The amino group canthen be introduced by e.g. reduction of a nitro group, displacement of ahalogen group by ammonia or hydrolysis of an amide.

The diazo moieties useful in the present invention have the formulae:##STR1## wherein up to two of the substituents R¹ through R¹³ on eachradical is a fluorinated ester group of the structure --Z--O--R whereinZ is either --CO-- or --SO₂ --, and R is a fluoroaliphatic radicalcontaining one to eighteen carbons, straight chain, branched chain oralicyclic, and which is partly or completely fluorinated; and otherwise:

R¹ is hydrogen, halogen, cyano, formyl, lower alkanoyl, benzoyl, loweralkoxycarbonyl, lower alkylsulfonyl, sulfamoyl, lower alkylsulfamoyl,carbamoyl, lower alkylcarbamoyl, or trifluoromethyl;

R² is halogen, cyano, lower alkylsulfonyl, formyl, lower alkanoyl,benzoyl, lower alkoxycarbonyl, sulfamoyl, lower alkylsulfamoyl,carbamoyl, lower alkylcarbamoyl, trifluoromethyl, or nitro;

R³ is hydrogen, halogen, cyano or nitro;

R⁶ is cyano, nitro, aryl, lower alkanoyl, aroyl, lower alkoxycarbonyl,lower hydroxyalkoxycarbonyl, lower alkoxy-lower-alkoxycarbonyl, or thegroup --CONR^(4') R^(5') in which R^(4') individually is hydrogen, loweralkyl, cyclohexyl, lower alkylcyclohexyl, cyclohexylmethyl, loweralkylcyclohexylmethyl, lower hydroxyalkylcyclohexylmethyl,aryl-lower-alkyl, or aryl; R^(5') individually is hydrogen or loweralkyl; and R^(4') and R^(5') in combination are pentamethylene orethyleneoxyethylene;

R⁵ is hydrogen, lower alkyl, lower alkoxy, aryl-lower-alkyl or aryl;

R⁴ is lower alkyl, halogen, thiocyanato, arylazo, or a group which R¹can represent;

R⁷ is hydrogen, lower alkyl, lower alkoxy, nitro, halogen, loweralkylsulfonyl, carbamoyl, lower alkylcarbamoyl, lower alkoxycarbonyl,sulfamoyl, lower alkylsulfamoyl, cyano, thiocyanato, trifluoromethyl,phenyl or substituted phenyl;

R⁸ is hydrogen, lower alkyl, lower alkoxy, nitro, halogen, loweralkylsulfonyl, substituted lower alkylsulfonyl, carbamoyl, loweralkylcarbamoyl, lower alkoxycarbonyl, sulfamoyl, lower alkylsulfamoyl,cyano, thiocyanato, lower alkylthio, cyclohexylthio, phenylthio,substituted phenylthio, or trifluoromethyl;

R⁹ and R¹⁰ are fluorinated ester groups as defined above by --Z--O--R;

R¹² is hydrogen, cyano, or lower alkyl;

R¹³ is cyano, carbamoyl, nitro, or lower alkoxycarbonyl;

R¹⁴ is hydrogen, lower alkyl, phenyl, phenyl substituted with halogen,lower alkyl, lower alkoxy, lower alkanoylamino, cyano, or loweralkoxycarbonyl, lower alkylsulfonyl, phenylsulfonyl, phenylsulfonylsubstituted with halogen, lower alkyl, lower alkoxy, loweralkanoylamino, cyano, or lower alkoxycarbonyl; and m is 1 or 2.

The couplers C' useful in the present invention have the formulae##STR2## wherein R¹⁵ and R¹⁶ are each selected from hydrogen, fluorine,chlorine, bromine, lower alkyl, cycloalkyl, lower alkoxy,trifluoromethyl, phenoxy, lower alkylthio, arylthio, and radicals havingthe formula --NH--X'--R²³ in which X' is --CO--, --COO--, or --SO₂ --and R²³ is selected from lower alkyl and lower alkyl substituted withhalogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, lower alkylsulfonyl,lower alkylthio, lower alkanoyloxy, and lower alkoxy, and when X' is--CO--, R²³ also can be hydrogen, amino, lower alkylamino, loweralkylcarbamoyl, lower dialkylamino, arylamino, aryl, furfuryl, or furyl;

R¹⁷ and R¹⁸ are selected from hydrogen; cycloalkyl; cycloalkylsubstituted with one or two groups selected from lower alkyl, --OH,lower alkoxy, halogen and hydroxy substituted lower alkyl; phenyl orphenyl substituted with lower alkyl, lower alkoxy, halogen, loweralkanoylamino, cyano or lower alkoxycarbonyl; straight or branched loweralkenyl; straight or branched alkyl of 1-8 carbons and such alkylsubstituted with 1-3 of the following: hydroxy; halogen; cyano;succinimido; glutarimido; phthalimido; 2-pyrrolidono; benzothiazolyl;cyclohexyl; phenyl or phenyl substituted with lower alkyl, lower alkoxy,halogen, lower alkanoylamino, cyano or lower alkoxycarbonyl; loweralkanoylamino; sulfamoyl; lower alkylsulfamoyl; vinylsulfonyl;acrylamido; phthalimidinyl; benzoylsulfonicimidyl; loweralkylsulfonamido; phenylsulfonamido; lower alkoxycarbonylamino; loweralkylcarbamoyloxy; lower alkoxycarbonyl; lower alkanoyloxy; loweralkoxycarbonyloxy; lower alkenylcarbonylamino; groups of the formula##STR3## wherein Y is --NH--, ##STR4## --O--, --S--, or --CH₂ O--;--S--R²⁴ wherein R²⁴ is lower alkyl, phenyl, phenyl substituted withhalogen, lower alkyl, lower alkoxy, lower alkanoylamino, cyano, or loweralkoxycarbonyl, pyridyl, pyrimidinyl, benzoxazolyl, benzimidazolyl,benzothiazolyl, triazolyl, or ##STR5## --SO₂ R²³ ; --COOR²³ ; --OX'R²³ ;--NH--X'--R²³ ; --X'--R²³ ; --OCO--R²³ ; --CONR²⁵ R²⁵ ; --SO₂ NR²⁵ R²⁵ ;wherein R²³ and X' are as defined above and each R²⁵ is selected from Hand R²³ ; lower alkoxy; lower alkoxy substituted with hydroxy, cyano,lower alkanoyloxy, or lower alkoxy; phenoxy; phenoxy substituted withone or more of lower alkyl, lowr alkoxy or halogen; or R¹⁷ and R¹⁸ canbe a single, combined group such as pentamethylene, ethyleneoxyethyleneand ethylenesulfonylethylene which, with the nitrogen atom to which itis attached, forms a ring;

R¹⁹, R²⁰, R²¹ and R²² are each selected from hydrogen and lower alkyl.The term "lower" are used herein means 1-6 carbons.

The couplers are prepared by procedures well known in the art and suchcouplers are disclosed in general in the patent literature, e.g., U.S.Pat. Nos. 2,805,218; 2,827,450; and 2,839,523.

In general the dyes of this invention are more bathochromic than thecorresponding dyes where the fluorine atoms are replaced by hydrogenatoms, they sublime more readily than their hydrogen analogues, brightershades are obtained when the dyes are heat transfer printed or dyed onthe fibre, and are quite stable even at the temperatures used in theheat transfer printing process (200°-210° C.). They are also stable tothe hydrolytic conditions used in the exhaust dyeing process. Thecorresponding hydrogen analogues are unstable even at room temperatureand are isolated only with difficulty.

The present dyes are made up into a printing ink formulation or anaqueous dispersion by conventional methods. For example, a printing inkformulation is prepared by ball milling the dye with ethyl cellulosebinder in ethanol for twentyfour hours. An aqueous dispersion forexhaust dyeing is prepared, for example, by ball milling the dye withREAX 80 C (anionic dispersing agent) and water until proper dispersionis achieved.

The following examples will further illustrate the invention.

EXAMPLE 1

Sodium nitrite (0.48 g) was added to concentrated sulphuric acid (3.5ml) and the solution heated to 70° C. for five minutes. Propionicacid-acetic acid (1:5) (7 ml) was added at below 20° C. The mixture wascooled to 0° C. and 4-amino-3,5-dibromo hexafluoroisopropyl phenylsulphonate (3.2 g) was added followed by a further 7 ml of 1:5 acid. Themixture was diazotised for one hour at 0°-5° C. and then added toN,N-diethyl m-toluidine (1.6 g) in ethanol with sodium acetate present.After twenty minutes the mixture was added to cold water and the dibromodye precipitated as a sticky solid. The crude dye was dissolved indimethylformamide (50 ml) and stirred at 110° C. with cuprous cyanide(2.5 g) for three hours. The mixture was poured into cold water and thesolid filtered off and extracted with hot ethyl acetate. The ethylacetate extract was concentrated to dryness and the residue slurriedwith warm isopropanol to give 2.5 g of the final dye product. ##STR6##

EXAMPLE 2

By the above procedure 4-amino-3,5-dibromohexafluoroisopropylphenylsulfonate was diazotised and coupled toN,N-diethyl-2-methoxy-5-trifluoroacetamido aniline and the cyanidedisplacement reaction carried out to give the greenish-blue dicyano dye.##STR7##

EXAMPLE 3

Using the above procedure 2-aminothiophene-3,5-bis-sulphonic acidbis-hexafluoro-isopropyl ester was diazotised and coupled toN-ethyl-2,2,4,7-tetramethyl-1,2,3,4-tetrahydroquinoline to give the bluedye. ##STR8##

The dyes from Examples 1-3 were applied by both the heat transferprinting process and by exhaust dyeing to polyester and nylon. Brightblue prints and dyeings were obtained which were of good strength andhad good fastness properties. The dyes had particularly good propertieson polyester fibres and especially good lightfastness. They weresurprisingly bathochromic in shade compared to the hydrogen analogues.

The dyes for Examples 1-3 also were used to prepare inks by thefollowing procedure. A sample of each dye was ball-milled in ethanol:ethylene glycol (9:1 by volume) with ethyl cellulose thickener for 48hours. The resulting ink was applied to pieces of flexographic paper byroller coating and allowed to dry. Pieces of the paper were then usedfor transfer printing onto nylon fabric at 200° C. for 30 seconds, andonto polyester fabric at 210° C. for 30 seconds. Bright blue prints wereobtained which were of good strength and had good fastness properties.

These dyes also were applied by exhaust dyeing as follows. An amount of0.1 g of the dye was dissolved in 10 ml of 2-methoxyethanol. A smallamount (3 to 5 ml) of a 3% sodium lignin sulphonate aqueous solution wasadded, with stirring and then the volume of the batch was brought to 300ml with water. 3 ml of an anionic solvent carrier (Tanavol) was added tothe bath and 10 g of a textile fabric (polyester) was placed in the bathand worked 10 minutes without heat. The dyeing was then carried out atthe boil for 1 hour. The dyed fabric was removed from the dyebath andscoured for 20 minutes at 80° C. in a solution containing 1 g/literneutral soap and 1 g/liter sodium carbonate. The fabric was then rinsed,dried in an oven at 121° C. and heat set (for the removal of residualcarrier) for 5 minutes at 177° C. The fabric was dyed a bright shade ofblue. The prints and dyeings from both the heat transfer process and theexhaust dyeing process were of good strength and had good fastnessproperties. The dyes had particularly good properties on polyesterfibres and especially good light fastness. They were surprisinglybathochromic in shade compared to the hydrogen analogues.

The following tables illustrate dyes of the present invention.

                                      TABLE 1                                     __________________________________________________________________________     ##STR9##                                                                        Dia-                                                                          zo                                                                            Moi-                                                                       Ex.                                                                              ety                                                                              Substituents     R.sup.15                                                                              R.sup.16                                                                           R.sup.17     R.sup.18                     __________________________________________________________________________    4  A  2,6-dicyano-4-(CF.sub.3).sub.2 CHOSO.sub.2                                                     NHCOCH.sub.3                                                                          H    CH.sub.2 CH.sub.3                                                                          CH.sub.2 CH.sub.2                                                             OCOCH.sub.3                  5  "  2,6-dicyano-4-CF.sub.3 CH.sub.2 OSO.sub.2                                                      "       "    "            "                            6  "  2,6-dicyano-4-CF.sub.3 CF.sub.2 CH.sub.2 OSO.sub.2                                             "       "    "            "                            7  "  2,6-dicyano-4-(CF.sub.3).sub.2 CHOCO                                                           "       "    "            "                            8  "  2,6-dicyano-4-CF.sub.3 CH.sub.2 OCO                                                            "       "    "            "                            9  "  2,6-dicyano-4-CF.sub.3 CF.sub.2 CH.sub.2 OCO                                                   "       "    "            "                            10 "  2,6-dicyano-4-(CF.sub.3).sub.2 CHOSO.sub.2                                                     "       OCH.sub.3                                                                          "            CH.sub.2 CH.sub.2 CN         11 "  "                H       "    CH.sub.2 CH.sub.2 OCOCH.sub.3                                                              CH.sub.2 CH.sub.2                                                             OCOCH.sub.3                  12 "  2,6-dinitro-4-(CF.sub.3).sub.2 CHOSO.sub.2                                                     NHCOCH.sub.3                                                                          H    CH.sub.2 CH.sub.2 CN                                                                       CH.sub.2 CH.sub.2 OH         13 "  2,6-dinitro-4-(CF.sub.3).sub.2 CHOCO                                                           "       "    "            CH.sub.2 CH.sub.2                                                             OCOCH.sub.3                  14 "  2,6-dicyano-4-(CF.sub.3).sub.2 CHOCO                                                           "       "    "            CH.sub.2 CH.sub.2 CN         15 "  2-cyano-4-(CF.sub.3).sub.2 CHOSO.sub.2                                                         "       "    CH.sub.2 CH.sub.3                                                                          CH.sub.2 CH.sub.2 OH         16 "  "                "       "    "                                                                                           ##STR10##                   17 B  3,5-bis-(CF.sub.3).sub.2 CHOSO.sub.2                                                           "       "    CH.sub.2 CH.sub.2 CN                                                                       CH.sub.2 CH.sub.2                                                             OCOC.sub.6 H.sub.5           18 "  3,5-bis-CF.sub.3 CH.sub.2 OSO.sub.2                                                            "       "    "            "                            19 "  3,5-bis-CF.sub.3 CF.sub.2 CH.sub.2 OSO.sub.2                                                   "       "    "            "                            20 "  3,5-bis-CF.sub.3 CH.sub.2 OCO                                                                  "       "    "            "                            21 "  3,5-bis-CF.sub.3 CF.sub.2 CH.sub.2 OCO                                                         "       "    "            "                            22 "  3-nitro-5-(CF.sub.3).sub.2 CHOSO.sub.2                                                         "       "    "            "                            23 "  3-nitro-5-CF.sub.3 CH.sub.2 OSO.sub.2                                                          "       "    "            "                            24 "  3-nitro-5-(CF.sub.3).sub.2 CHOCO                                                               "       "    "            "                            25 "  3-nitro-5-(CF.sub.3).sub.2 CHOCO                                                               "       "    "            "                            26 "  3-(CF.sub.3).sub.2 CHOSO.sub.25NO.sub.2                                                        "       "    "            "                            27 "  3-(CF.sub.3).sub.2 CHOCO5NO.sub.2                                                              "       "    "            "                            28 "  3,5-bis-(CF.sub.3 ).sub.2 CHOCO                                                                "       "    "            CH.sub.2 CH.sub.2                                                             CH.sub.2 CH.sub.3            29 "  "                "       "    CH.sub.2 CH.sub.3                                                                          CH.sub.2 C.sub.6                                                              H.sub.5                      30 "  "                "       "    C.sub.6 H.sub.11                                                                            ##STR11##                   31 "  "                "       "    "            CH.sub.2 CH.sub.2 OH         32 I  3-(CF.sub. 3).sub.2 CHOSO.sub.2                                                                "       "    "            CH.sub.2 CH.sub.3            33 "  3-(CF.sub.3).sub.2 CHOCO                                                                       "       "    CH.sub.2 CH.sub.3                                                                          "                            34 C  5-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 "       "    CH.sub.2 CH.sub.2 OCH.sub.3                                                                 ##STR12##                   35 "  6-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 "       "    "            "                            36 "  6-CF.sub.3 CH.sub.2 OSO.sub.2                                                                  "       "    "            "                            37 "  6-(CF.sub.3).sub.2 CHOCO                                                                       "       "    "            "                            38 "  6-CF.sub.3 CH.sub.2 OCO                                                                        "       "    "            "                            39 "  6-CF.sub.3 CF.sub.2 CH.sub.2 OCO                                                               "       "    "            "                            40 "  5-(CF.sub.3).sub.2 CHOCO                                                                       CH.sub.3                                                                              "    CH.sub.2 CH.sub.2 OH                                                                       CH.sub.2 CH.sub.2 OH         41 "  "                "       "    "            CH.sub.2 CH.sub.3            42 "  "                "       "    CH.sub.2 CH.sub.2 OCOCH.sub.3                                                              CH.sub.2 CH.sub.2                                                             OCOCH.sub.3                  43 "  "                "       "    CH.sub.2 CH.sub.3                                                                           ##STR13##                   44 "  "                "       "    "            CH.sub.2 CH.sub.2 CN         45 C  5-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 "       "    "            CH.sub.2 CH.sub.2 Cl         46 "  5-(CF.sub.3).sub.2 CHOSO.sub. 2                                                                "       "    "            "                            47 "  5-(CF.sub.3).sub.2 CHOCO                                                                       "       "    "            "                            48 "  5-CF.sub.3 CH.sub.2 OCO                                                                        "       "    "            "                            49 "  5-(CF.sub.3).sub.2 CHOCO                                                                       "       "    "            CH.sub.2 CH.sub.2                                                             OCOCH.sub.3                  50 "  "                "       "    CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2                                           CH.sub.2                                  51 "  "                NHCOCH.sub.3                                                                          "    CH.sub.2 CH.sub.3                                                                          CH.sub.2 CH.sub.3            52 "  "                "       "    "            CH.sub.2 CH.sub.2 CN         53 D  6-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 "       "    CH.sub.2 CH.sub.2 OCOCH.sub.3                                                              CH.sub.2 CH.sub.2                                                             OCOCH.sub.3                  54 "  6-CF.sub.3 CH.sub.2 OSO.sub.2                                                                  "       "    "            "                            55 "  6-CF.sub.3 CH.sub.2 OCO                                                                        "       "    "            "                            56 "  5-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 "       "    "            "                            57 "  5-CF.sub.3 CH.sub.2 OCO                                                                        "       "    "            "                            58 "  5-Cl6-(CF.sub.3).sub.2 CHOSO.sub.2                                                             "       "    "            "                            59 "  6-(CF.sub.3).sub.2 CHOCO                                                                       "       CH.sub.3                                                                           H            CH.sub.2 CH.sub.2 CN         60 "  "                "       "    "            CH(CH.sub.3)CH.sub.2                                                          CH.sub.3                     61 "  "                H       OCH.sub.3                                                                          H                                                                                           ##STR14##                   62 "  "                CH.sub.3                                                                              H    CH.sub.2 CH.sub.3                                                                          CH.sub.2 CH.sub.2                                                             SO.sub.2 NH.sub.2            63 H  4-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 NHCOCH.sub.3                                                                          H    H                                                                                           ##STR15##                   64 "  4-CF.sub.3 CH.sub.2 OSO.sub.2                                                                  "       "    "            "                            65 "  4-CF.sub.3 CH.sub.2 OCO                                                                        "       "    "            "                            66 "  4-(CF.sub.3).sub.2 CHOCO                                                                       "       "    "            CH.sub.2 CH.sub.2                                                             OCH.sub.3                    67 "  "                "       "    "                                                                                           ##STR16##                   68 E  4-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 "       "    "                                                                                           ##STR17##                   69 "  5-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 "       "    "            "                            70 "  5-CF.sub.3 CH.sub.2 OSO.sub.2                                                                  "       "    "            "                            71 "  5-(CF.sub.3).sub.2 CHOCO                                                                       "       "    "            "                            72 "  5-CF.sub.3 CH.sub.2 OCO                                                                        "       "    "            "                            73 "  4-(CF.sub.3).sub.2 CHOCO                                                                       "       "    "                                                                                           ##STR18##                   74 "  "                "       "    "            CH(CH.sub.3)CH.sub.2                                                          CH.sub.3                     75 A  2,6-dicyano-4-(CF.sub.3).sub.2 CHOSO.sub.2                                                     H       CH.sub.3                                                                           "                                                                                           ##STR19##                   76 "  2,6-dicyano-4-(CF.sub.3).sub.2 CHOCO                                                           H       H    H            CH.sub.2 CH.sub.2 CN         77 "  2,6-dinitro-4-(CF.sub.3).sub.2 CHOCO                                                           "       "    CH.sub.3     CH.sub.3                     78 "  "                "       "    CH.sub.2 CH.sub.3                                                                          CH.sub.2 CH.sub.3            79 "  "                "       "    "            CH.sub.2 C.sub.6                                                              H.sub.5                      80 "  "                "       "    "            C.sub.6 H.sub.11             81 "  "                "       "    "            CH.sub.2 CH.sub.2 OH         82 F  3-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 "       "    "            CH.sub.2 CH.sub.2                                                             OCOCH.sub.3                  83 "  4-(CF.sub.3).sub.2 CHOSO.sub.2 3-chloro                                                        "       "    "            "                            84 "  4-CF.sub.3 CH.sub.2 OSO.sub.2 3-chloro                                                         "       "    "            "                            85 "  3-(CF.sub.3).sub.2 CHOCO                                                                       "       "    "            CH.sub.2 CH(OH)CH.sub. 2                                                      OH                           86 "  "                "       "    "            CH.sub.2 CH.sub.3 CN         87 "  "                "       "    CH.sub.2 CH.sub.3 CN                                                                       "                            88 "  "                "       "    "            CH.sub.2 CH.sub.2 OH         89 "  "                "       "    "            CH.sub.2 CH.sub.2                                                             OCOCH.sub.3                  90 B  3,5-bis-(CF.sub.3).sub.2 CHOSO.sub.2                                                           "       "    "            CH.sub.2 CH.sub.2                                                             OCOC.sub.6 H.sub.5           91 "  3,5-bis-(CF.sub.3).sub.2 CHOCO                                                                 "       "    CH.sub.2 CH.sub.2 OH                                                                       CH.sub.2 CH.sub.2 OH         92 "  "                "       "    CH.sub.2 CH.sub.2 OCOCH.sub.3                                                              CH.sub.2 CH.sub.2                                                             OCOCH.sub.3                  93 "  "                "       "    CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2                                           CH.sub.2                                  94 G  5-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 Cl      Cl   H            CH.sub.2 CH.sub.2 CN         95 "  5-(CF.sub.3).sub.2 CHOCO                                                                       CH.sub.3                                                                              H    CH.sub.2 CH.sub.3                                                                           ##STR20##                   96 C  5-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 CH.sub.3                                                                              H    "            CH.sub.2 CH.sub.3            97 "  5-(CF.sub.3).sub.2 CHOCO                                                                       "       "    "            CH.sub.2 CH.sub.2 OH         98 "  "                "       "    "            CH.sub.2 CH.sub.2                                                             NH.sub.2                     99 H  4-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 "       "    CH.sub.2 CH.sub.3                                                                          "                            100                                                                              "  4-(CF.sub.3).sub.2 CHOCO                                                                       "       "    CH.sub.2 CH.sub.2 CN                                                                       "                            101                                                                              "  "                NHCOCH.sub.3                                                                          "    CH.sub.2 CH.sub.3                                                                          CH.sub.2 CH.sub.3            102                                                                              "  "                "       "    "            CH.sub.2 CH.sub.2                                                             OCOCH.sub.3                  103                                                                              "  "                "       "    "            (CH.sub.2 CH.sub.2                                                            O).sub.2 CH.sub.2                                                             CH.sub.3                     104                                                                              D  6-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 NHCOC.sub.6 H.sub.5                                                                   "    "            CH.sub.2 CH.sub.2                                                             CONH.sub. 2                  105                                                                              "  6-(CF.sub.3).sub.2 CHOCO                                                                       "       CH.sub.3                                                                           H            CH.sub.2 CH.sub.3            106                                                                              "  "                NHCOCH.sub.3                                                                          OCH.sub.3                                                                          CH.sub.2 CH.sub.3                                                                          "                            107                                                                              "  "                "       "    "            CH.sub.2 CH.sub.3                                                             OCOCH.sub.3                  108                                                                              I  3-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 "       "    "            CH.sub.2 CH(OH)CH.sub.3      109                                                                              "  3-CF.sub.3 CH.sub.2 OSO.sub.2                                                                  "       "    "            "                            110                                                                              "  3-CF.sub.3 CH.sub.2 OCO                                                                        "       "    "            "                            111                                                                              "  3-(CF.sub.3).sub.2 CHOCO                                                                       "       "    CH.sub.2 CH.sub.2 OH                                                                       CH.sub.2 CH.sub.2 OH         112                                                                              "  "                "       "    CH.sub.2 CH.sub.2 OCOCH.sub.3                                                              CH.sub.2 CH.sub.2                                                             OCOCH.sub.3                  113                                                                              "  "                "       "    CH.sub.2 CH.sub.3                                                                           ##STR21##                   114                                                                              "  "                "       "    CH.sub.2 CH.sub.3                                                                           ##STR22##                   115                                                                              "  "                "       "    "                                                                                           ##STR23##                   __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________     ##STR24##                                                                       Diazo                                                                      Ex.                                                                              Moiety                                                                            Substituents      R.sup.15, R.sup.16, R.sup.19, R.sup.20,                                       R.sup.21, R.sup.22                                                                           R.sup.17                              __________________________________________________________________________    116                                                                              A   2,6-dicyano-4-(CF.sub.3).sub.3 CHOSO.sub.2                                                      2,7-di-CH.sub.3                                                                              C.sub.2 H.sub.4 OH                    117                                                                              "   2,6-dicyano-4-CF.sub.3 CH.sub.2 OSO.sub.2                                                       "              "                                     118                                                                              "   2,6-dicyano-4-CF.sub.3 CF.sub.2 CH.sub.2 OSO.sub.2                                              "              "                                     119                                                                              "   2,6-dicyano-4-(CF.sub.3).sub.2 CHOCO                                                            "              "                                     120                                                                              "   2,6-dicyano-4-CF.sub.3 CH.sub.2 OCO                                                             "              "                                     121                                                                              "   2,6-dicyano-4-CF.sub.3 CF.sub.2 CH.sub.2 OCO                                                    "              "                                     122                                                                              "   2,6-dicyano-4-(CF.sub. 3).sub.2 CHOCO                                                           2,5-di-CH.sub.38-OCH.sub.3                                                                   CH.sub.2 CH(OH)CH.sub.2 OH            123                                                                              "   2,6-dinitro-4-(CF.sub.3).sub.2 CHOCO                                                            2,2,4,7-tetra-CH.sub.3                                                                       C.sub.2 H.sub.4 CONH.sub.2            124                                                                              "   "                 2,2,4-tri-CH.sub.3                                                                           C.sub.2 H.sub.4 NHCOCH.sub.3          125                                                                              I   3-(CF.sub.3).sub.2 CHOSO.sub.2                                                                  2-CH.sub.37-NHCOCH.sub.3                                                                     C.sub.2 H.sub.4 CN                    126                                                                              "   "                 "              "                                     127                                                                              "   3-CF.sub.3 CH.sub.2 OCO                                                                         "              "                                     128                                                                              "   3-(CF.sub.3).sub.2 CHCO                                                                         2,2,4-tri-CH.sub.37-NHCOCH.sub.3                                                             C.sub.2 H.sub.4 Cl                    129                                                                              "   "                 2,-CH(CH.sub. 3).sub.27-NHCOCH.sub.3                                                         C.sub.2 H.sub.4 OOCCH.sub.3           130                                                                              "   "                 7-CH.sub.3     C.sub.2 H.sub.4 OC.sub.2 H.sub.5      131                                                                              B   3,5-bis-(CF.sub.3).sub.2 CHOSO.sub.2                                                            3-CN7-CH.sub.3 C.sub.2 H.sub.4 CONHC.sub.2                                                   H.sub.5                               132                                                                              "   3,5-bis-CF.sub.3 CH.sub.2 OSO.sub.2                                                             "              "                                     133                                                                              "   3,5-bis-CF.sub.3 CF.sub.2 CH.sub.2 OSO.sub.2                                                    "              "                                     134                                                                              "   3,5-bis-CF.sub.3 CH.sub. 2 OCO                                                                  "              "                                     135                                                                              "   3,5-bis-CF.sub.3 CF.sub.2 CH.sub.2 OCO                                                          "              "                                     136                                                                              "   3-nitro-5-(CF.sub.3).sub.2 CHOSO.sub.2                                                          "              "                                     137                                                                              "   3-nitro-5-CF.sub.3 CH.sub.2 OSO.sub.2                                                           "              "                                     138                                                                              "   3-nitro-5-(CF.sub.3).sub.2 CHOCO                                                                "              "                                     139                                                                              "   3-nitro-5-(CF.sub.3).sub.2 CHOCO                                                                "              "                                     140                                                                              "   3-(CF.sub.3).sub.2 CHOSO.sub.25-NO.sub.2                                                        "              "                                     141                                                                              "   3-(CF.sub.3).sub.2 CHOCO5-NO.sub.2                                                              "              "                                     142                                                                              "   3,5-bis-(CF.sub.3).sub.2 CHOCO                                                                  3-CONH.sub.27-CH.sub.3                                                                       C.sub.2 H.sub.4 CONHC.sub.2                                                   H.sub.5                               143                                                                              "   "                 3-Cl7-CH.sub.3 C.sub.2 H.sub.4 CONHCH.sub.2                                                  C.sub.6 H.sub.5                       144                                                                              "   "                 3-OCH.sub.37-CH.sub.3                                                                        C.sub.2 H.sub.4 OOCOC.sub.2                                                   H.sub.5                               145                                                                              "   "                 2,2,4-di-CH.sub.35,8-di-OCH.sub.3                                                            C.sub.2 H.sub.4 NHCOCHCH.sub.2        146                                                                              H   4-(CF.sub.3).sub.2 CHOSO.sub.2                                                                  2,2,4-tri-CH.sub.38-OCH.sub.3                                                                CH.sub.2 C.sub.6 H.sub.5              147                                                                              "   4-CF.sub.3 CH.sub.2 OSO.sub.2                                                                   "              "                                     148                                                                              "   4-CF.sub.3 CH.sub.2 OCO                                                                         "              "                                     149                                                                              "   4-(CF.sub.3).sub.2 CHOCO                                                                        2-CH.sub.37-NHCOCH.sub.3                                                                     C.sub.2 H.sub.4 CONHCH.sub.2 OH       150                                                                              "   "                 3-OH7-CH.sub.3 C.sub.3 H.sub.6 NHCONHC.sub.2                                                 H.sub.5                               151                                                                              "   "                 2,7-di-CH.sub.3                                                                              C.sub.2 H.sub.5                       152                                                                              C   5-(CF.sub.3).sub.2 CHOSO.sub.2                                                                  2,5-di-CH.sub.38-OCH.sub.3                                                                   C.sub.2 H.sub.4 SO.sub.2 NH.sub.2                                             8                                     153                                                                              "   6-(CF.sub.3).sub.2 CHOSO.sub.2                                                                  "              "                                     154                                                                              "   6-CF.sub.3 CH.sub.2 OSO.sub.2                                                                   "              "                                     155                                                                              "   6-(CF.sub.3).sub.2 CHOCO                                                                        "              "                                     156                                                                              "   6-CF.sub.3 CH.sub.2 OCO                                                                         "              "                                     157                                                                              "   6-CF.sub.3 CF.sub.2 CH.sub.2 OCO                                                                "              "                                     158                                                                              "   5-(CF.sub.3).sub.2 CHOCO                                                                        2,2,4,7-tetra-CH.sub.3                                                                       C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2                                             H.sub.5                              159                                                                              "   "                 2,2,4-tri-CH.sub.3                                                                           C.sub.2 H.sub.4 SCH.sub.3             160                                                                              C   5-(CF.sub.3).sub.2 CHOSO.sub.2                                                                  2-CH.sub.37-NHCOCH.sub.3                                                                      ##STR25##                            161                                                                              D   6-(CF.sub.3).sub.2 CHOSO.sub.2                                                                  2,2,4-tri-CH.sub.37-NHCOCH.sub.3                                                              ##STR26##                            162                                                                              "   6-CF.sub.3 CH.sub.2 OSO.sub.2                                                                   "              "                                     163                                                                              "   6-CF.sub.3 CH.sub.2 OCO                                                                         "              "                                     164                                                                              "   5-(CF.sub.3).sub.2 CHOSO.sub.2                                                                  "              "                                     165                                                                              "   5-CF.sub.3 CH.sub.2 OCO                                                                         "              "                                     166                                                                              "   5-Cl6-(CF.sub.3).sub.2 CHOSO.sub.2                                                              "              "                                     167                                                                              "   6-(CF.sub.3).sub.2 CHOCO                                                                        2-CH(CH.sub.3).sub.27-NHCOCH.sub.3                                                            ##STR27##                            168                                                                              "   "                 7-CH.sub.3                                                                                    ##STR28##                            169                                                                              F   3-(CF.sub.3).sub.2 CHOSO.sub.2                                                                  3-CN7-CH.sub.3                                                                                ##STR29##                            170                                                                              "   4-(CF.sub.3).sub.2 CHOSO.sub.23-chloro                                                          "              "                                     171                                                                              "   4-CF.sub.3 CH.sub.2 OSO.sub.23-chloro                                                           "              "                                     172                                                                              "   3-(CF.sub.3).sub.2 CHOCO                                                                        3-CONH.sub.27-CH.sub.3                                                                        ##STR30##                            173                                                                              A   2,6-dicyano-4-(CF.sub.3).sub.2 CHOSO.sub.2                                                      3-Cl7-CH.sub.3                                                                                ##STR31##                            174                                                                              E   4-(CF.sub.3).sub.2 CHOSO.sub.2                                                                  3-OCH.sub.37-CH.sub.3                                                                         ##STR32##                            175                                                                              "   5-(CF.sub.3).sub.2 CHOSO.sub.2                                                                  "              "                                     176                                                                              "   5-CF.sub.3 CH.sub.2 OSO.sub.2                                                                   "              "                                     177                                                                              "   5-(CF.sub.3).sub. 2 CHOCO                                                                       "              "                                     178                                                                              "   5-CF.sub.3 CH.sub.2 OCO                                                                         "              "                                     179                                                                              "   4-(CF.sub.3).sub.2 CHOCO                                                                        2,2,4-di-CH.sub.35,8-di-OCH.sub.3                                                             ##STR33##                            180                                                                              B   3,5-bis-(CF.sub.3).sub.2 CHOSO.sub.2                                                            2,2,4-tri-CH.sub.38-OCH.sub.3                                                                 ##STR34##                            181                                                                              "   3,5-bis-(CF.sub.3).sub.2 CHOCO                                                                  2-CH.sub.37-NHCOCH.sub.3                                                                      ##STR35##                            182                                                                              F   3-(CF.sub.3).sub.2 CHOSO.sub.2                                                                  3-OH7-CH.sub.3                                                                                ##STR36##                            183                                                                              C   5-(CF.sub.3).sub.2 CHOSO.sub.2                                                                  2,7-di-CH.sub.3                                                                               ##STR37##                            184                                                                              G   5-(CF.sub.3).sub.2 CHOSO.sub.2                                                                  2,5-di-CH.sub.38-OCH.sub.3                                                                    ##STR38##                            185                                                                              "   5-(CF.sub.3).sub.2 CHOSO.sub.2                                                                  "              "                                     186                                                                              "   5-(CF.sub.3).sub.2 CHOCO                                                                        "              "                                     187                                                                              "   5-CF.sub.3 CH.sub.2 OCO                                                                         "              "                                     188                                                                              "   5-(CF.sub.3).sub.2 CHOCO                                                                        2,2,4,7-tetra-CH.sub.3                                                                        ##STR39##                            189                                                                              "   "                 2,2,4-tri-CH.sub.3                                                                            ##STR40##                            190                                                                              H   4-(CF.sub.3).sub.2 CHOSO.sub.2                                                                  2-CH.sub.37-NHCOCH.sub.3                                                                      ##STR41##                            191                                                                              D   6-(CF.sub.3).sub.2 CHOSO.sub.2                                                                  2,2,4-tri-CH.sub.37-NHCOCH.sub.3                                                              ##STR42##                            192                                                                              "   6-(CF.sub.3).sub.2 CHOCO                                                                        2-CH(CH.sub.3).sub.27-NHCOCH.sub.3                                                            ##STR43##                            193                                                                              I   3-(CF.sub.3).sub.2 CHOSO.sub.2                                                                  7-CH.sub.3                                                                                    ##STR44##                            194                                                                              "   3-(CF.sub.3).sub.2 CHOCO                                                                        3-CN7-CH.sub.3 C.sub.2 H.sub.4 OH                    195                                                                              "   "                 3-CONH.sub.27-CH.sub.3                                                                        ##STR45##                            196                                                                              "   "                 2,2,4,7-tetra-CH.sub. 3                                                                       ##STR46##                            197                                                                              "   "                 2,2,4,7-tetra-CH.sub.3                                                                        ##STR47##                            __________________________________________________________________________

                                      TABLE III                                   __________________________________________________________________________     ##STR48##                                                                       Diazo                                                                      Ex.                                                                              Moiety                                                                            Substituents     R.sup.15, R.sup.16, R.sup.19                                                             R.sup.17                                   __________________________________________________________________________    198                                                                              A   2,6-dicyano-4-(CF.sub.3).sub.2 CHOSO.sub.2                                                     3,6-di-CH.sub.3                                                                          C.sub.2 H.sub.4 OH                         199                                                                              "   2,6-dicyano-4-CF.sub.3 CH.sub.2 OSO.sub.2                                                      "          "                                          200                                                                              "   2,6-dicyano-4-CF.sub.3 CF.sub.2 CH.sub.2 OSO.sub.2                                             "          "                                          201                                                                              "   2,6-dicyano-4-(CF.sub.3).sub.2 CHOCO                                                           "          "                                          202                                                                              "   2,6-dicyano-4-CF.sub.3 CH.sub.2 OCO                                                            "          "                                          203                                                                              "   2,6-dicyano-4-CF.sub.3 CF.sub.2 CH.sub.2 OCO                                                   "          "                                          204                                                                              "   2,6-dicyano-4-(CF.sub.3).sub.2 CHOCO                                                           3-CH.sub.3 CH.sub.2 CH(OH)CH.sub.2 OH                 205                                                                              "   2,6-dinitro-4-(CF.sub.3).sub.2 CHOCO                                                           3-CH.sub.36-NHCOCH.sub.3                                                                 C.sub.2 H.sub.4 CONH.sub.2                 206                                                                              "   "                6-NHCOCH.sub.3                                                                           C.sub.2 H.sub.4 NHCOCH.sub.3               207                                                                              I   3-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 3,6-di-CH.sub.3                                                                          C.sub.2 H.sub.4 CN                         208                                                                              "   3-CF.sub.3 CH.sub.2 OSO.sub.2                                                                  "          "                                          209                                                                              "   3-CF.sub.3 CH.sub.2 OCO                                                                        "          "                                          210                                                                              "   3-(CF.sub.3).sub.2 CHOCO                                                                       3-CH.sub.3 C.sub.2 H.sub.4 Cl                         211                                                                              "   "                3-CH.sub.36-NHCOCH.sub.3                                                                 C.sub.2 H.sub.4 OOCC.sub.2 H.sub.5         212                                                                              "   "                6-NHCOCH.sub.3                                                                           C.sub.2 H.sub.4 OC.sub.2 H.sub.5           213                                                                              B   3,5-bis-(CF.sub.3).sub.2 CHOSO.sub.2                                                           3,6-di-CH.sub.3                                                                          C.sub.2 H.sub.4 CONHC.sub.2 H.sub.5        214                                                                              "   3,5-bis-CF.sub.3 CH.sub.2 OSO.sub.2                                                            "          "                                          215                                                                              "   3,5-bis-CF.sub.3 CF.sub.2 CH.sub.2 OSO.sub.2                                                   "          "                                          216                                                                              "   3,5-bis-CF.sub.3 CH.sub.2 OCO                                                                  "          "                                          217                                                                              "   3,5-bis-CF.sub.3 CF.sub.2 CH.sub.2 OCO                                                         "          "                                          218                                                                              "   3-nitro-5-(CF.sub.3).sub.2 CHOSO.sub.2                                                         "          "                                          219                                                                              "   3-nitro-5-CF.sub.3 CH.sub.2 OSO.sub.2                                                          "          "                                          220                                                                              "   3-nitro-5-(CF.sub.3).sub.2 CHOCO                                                               "          "                                          221                                                                              "   3-nitro-5-(CF.sub.3).sub.2 CHOCO                                                               "          "                                          222                                                                              "   3-(CF.sub.3).sub.2 CHOSO.sub.25-NO.sub.2                                                       "          "                                          223                                                                              "   3-(CF.sub.3).sub.2 CHOCO5-NO.sub.2                                                             "          "                                          224                                                                              "   3,5-bis-(CF.sub.3).sub.2 CHOCO                                                                 3-CH.sub.3 C.sub.2 H.sub.4 CONHC.sub.2 H.sub.5        225                                                                              "   "                3-CH.sub.36-NHCOCH.sub.3                                                                 C.sub.2 H.sub.4 CONHCH.sub.2 C.sub.6                                          H.sub.5                                    226                                                                              H   4-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 6-NHCOCH.sub.3                                                                           C.sub.2 H.sub.4 OOCOC.sub.2 H.sub.5        227                                                                              "   4-CF.sub.3 CH.sub.2 OSO.sub.2                                                                  "          "                                          228                                                                              "   4-CF.sub.3 CH.sub.2 OCO                                                                        "          "                                          229                                                                              "   4-(CF.sub.3).sub.2 CHOCO                                                                       3,6-di-CH.sub.3                                                                          C.sub.2 H.sub.4 NHCOCHCH.sub.2             230                                                                              "   "                3-CH.sub.3 CH.sub.2 C.sub.6 H.sub.5                   231                                                                              "   "                3-CH.sub.36-NHCOCH.sub.3                                                                 C.sub.2 H.sub.4 CONHCH.sub.2 OH            232                                                                              C   5-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 3,6-NHCOCH.sub.3                                                                         C.sub.3 H.sub.6 NHCONHC.sub.2 H.sub.5      233                                                                              "   6-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 "          "                                          234                                                                              "   6-CF.sub.3 CH.sub.2 OSO.sub.2                                                                  "          "                                          235                                                                              "   6-(CF.sub.3).sub.2 CHOCO                                                                       "          "                                          236                                                                              "   6-CF.sub.3 CH.sub.2 OCO                                                                        "          "                                          237                                                                              "   6-CF.sub.3 CF.sub.2 CH.sub.2 OCO                                                               "          "                                          238                                                                              "   5-(CF.sub.3).sub.2 CHOCO                                                                       3,6-di-CH.sub.3                                                                          C.sub.2 H.sub.5                            239                                                                              "   "                3-CH.sub.3 C.sub.2 H.sub.4 SO.sub.2 NH.sub.2          240                                                                              "   "                3-CH.sub.36-NHCOCH.sub.3                                                                 C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2                                            H.sub.5                                    241                                                                              G   5-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 6-NHCOCH.sub.3                                                                           C.sub.2 H.sub.4 SCH.sub.3                  242                                                                              "   5-(CF.sub.3).sub.2 CHOCO                                                                       3,6-di-CH.sub. 3                                                                          ##STR49##                                 243                                                                              D   6-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 3-CH.sub.3                                                                                ##STR50##                                 244                                                                              "   6-CF.sub.3 CH.sub.2 OSO.sub.2                                                                  "          "                                          245                                                                              "   6-CF.sub.3 CH.sub.2 OCO                                                                        "          "                                          246                                                                              "   5-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 "          "                                          247                                                                              "   5-CF.sub.3 CH.sub.2 OCO                                                                        "          "                                          248                                                                              "   5-Cl6-(CF.sub.3).sub.2 CHOSO.sub.2                                                             "          "                                          249                                                                              "   6-(CF.sub.3).sub.2 CHOCO                                                                       3-CH.sub.36-NHCOCH.sub.3                                                                  ##STR51##                                 250                                                                              A   2,6-dicyano-4-(CF.sub.3).sub.2 CHOSO.sub.2                                                     6-NHCOCH.sub.3                                                                            ##STR52##                                 251                                                                              "   2,6-dicyano-4-(CF.sub.3).sub.2 CHOCO                                                           3,6-di-CH.sub. 3                                                                          ##STR53##                                 252                                                                              "   2,6-dinitro-4-(CF.sub.3).sub.2 CHOCO                                                           3-CH.sub.3                                                                                ##STR54##                                 253                                                                              E   4-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 3-CH.sub.36-NHCOCH.sub.3                                                                  ##STR55##                                 254                                                                              "   5-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 "          "                                          255                                                                              "   5-CF.sub.2 CH.sub.2 OSO.sub.2                                                                  "          "                                          256                                                                              "   5-(CF.sub.3).sub.2 CHOCO                                                                       "          "                                          257                                                                              "   5-CF.sub.3 CH.sub.2 OCO                                                                        "          "                                          258                                                                              "   "                6-NHCOCH.sub.3                                                                            ##STR56##                                 259                                                                              B   3,5-bis-(CF.sub.3).sub.2 CHOSO.sub.2                                                           3,6-di-CH.sub.3                                                                           ##STR57##                                 260                                                                              "   3-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 3-CH.sub.3                                                                                ##STR58##                                 261                                                                              "   4-(CF.sub.3).sub.2 CHOSO.sub.23-chloro                                                         "          "                                          262                                                                              "   4-CF.sub.3 CH.sub.2 OSO.sub.23-chloro                                                          "          "                                          263                                                                              "   3-(CF.sub.3).sub.2 CHOCO                                                                       3-CH.sub.36-NHCOCH.sub.3                                                                  ##STR59##                                 264                                                                              C   5-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 6-NHCOCH.sub.3                                                                            ##STR60##                                 265                                                                              G   5-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 3,6-di-CH.sub.3                                                                           ##STR61##                                 266                                                                              "   5-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 "          "                                          267                                                                              "   5-(CF.sub.3).sub.2 CHOCO                                                                       "          "                                          268                                                                              "   5-CF.sub.3 CH.sub.2 OCO                                                                        "          "                                          269                                                                              "   5-(CF.sub.3).sub.2 CHOCO                                                                       3-CH.sub.3                                                                                ##STR62##                                 270                                                                              "   "                3-CH.sub.36-NHCOCH.sub.3                                                                  ##STR63##                                 271                                                                              H   4-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 6-NHCOCH.sub.3                                                                            ##STR64##                                 272                                                                              "   4-(CF.sub.3).sub.2 CHOCO                                                                       3,6-di-CH.sub.3                                                                           ##STR65##                                 273                                                                              "   "                3-CH.sub.3                                                                                ##STR66##                                 274                                                                              I   3-(CF.sub.3).sub.2 CHOSO.sub.2                                                                 3-CH.sub.36-NHCOCH.sub.3                                                                  ##STR67##                                 275                                                                              "   3-(CF.sub.3).sub.2 CHOCO                                                                       6-NHCOCH.sub.3                                                                            ##STR68##                                 276                                                                              "   "                3,6-di-CH.sub.3                                                                          C.sub.2 H.sub.4 OH                         277                                                                              "   "                3-CH.sub.3                                                                                ##STR69##                                 278                                                                              "   "                3,6-di-CH.sub.3                                                                           ##STR70##                                 279                                                                              "   "                3,6-di-CH.sub.3                                                                           ##STR71##                                 __________________________________________________________________________

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

I claim:
 1. An azo compound of the structure X--N═N--C' wherein X isselected from ##STR72## wherein one or two substituents R¹ through R¹³on each radical is an ester group of the structure --Z--O--R wherein Zis either ##STR73## and R is a lower alkyl group, straight chain,branched chain or alicyclic, and which is substituted with 1-3 fluorineatoms;R¹ is hydrogen, halogen, cyano, nitro, formyl, lower alkanoyl,benzoyl, lower alkoxycarbonyl, lower alkylsulfonyl, sulfamoyl, loweralkylsulfamoyl, carbamoyl, lower alkylcarbamoyl, or trifluoromethyl; R²is halogen, cyano, lower alkylsulfonyl, formyl, lower alkanoyl, benzoyl,lower alkoxycarbonyl, sulfamoyl, lower alkylsulfamoyl, carbamoyl, loweralkylcarbamoyl, trifluoromethyl, or nitro; R³ is hydrogen, halogen,cyano or nitro; R⁶ is cyano, nitro, aryl, lower alkanoyl, aroyl, loweralkoxycarbonyl, lower hydroxyalkoxycarbonyl, loweralkoxy-lower-alkoxycarbonyl, or the group 13 CONR^(4') R^(5') in whichR^(4') individually is hydrogen, lower alkyl, cyclohexyl, loweralkylcyclohexyl, cyclohexylmethyl, lower alkylcyclohexylmethyl, lowerhydroxyalkylcyclohexylmethyl, aryl-lower-alkyl, or aryl; R^(5')individually is hydrogen or lower alkyl; and R^(4') and R^(5') incombination are pentamethylene or ethyleneoxyethylene; R⁵ is hydrogen,lower alkyl, lower alkoxy, aryl-lower-alkyl or aryl; R⁴ is selected fromR¹, lower alkyl, thiocyanato and arylazo; R⁷ is hydrogen, lower alkyl,lower alkoxy, nitro, halogen, lower alkylsulfonyl, carbamoyl, loweralkylcarbamoyl, lower alkoxycarbonyl, sulfamoyl, lower alkylsulfamoyl,cyano, thiocyanato, trifluoromethyl or phenyl; R⁸ is hydrogen, loweralkyl, lower alkoxy, nitro, halogen, lower alkylsulfonyl, substitutedlower alkylsulfonyl, carbamoyl, lower alkylcarbamoyl, loweralkoxycarbonyl, sulfamoyl, lower alkylsulfamoyl, cyano, thiocyanato,lower alkylthio, cyclohexylthio, phenylthio or trifluoromethyl; R⁹ andR¹⁰ are fluorinated ester groups of the formula --Z--O--R; R¹² ishydrogen, cyano, or lower alkyl; R¹³ is cyano, carbamoyl, nitro, orlower alkoxycarbonyl; R¹⁴ is hydrogen, lower alkyl, phenyl, phenylsubstituted with halogen, lower alkyl, lower alkoxy, loweralkanoylamino, cyano, or lower alkoxycarbonyl, lower alkylsulfonyl,phenylsulfonyl, phenylsulfonyl substituted with halogen, lower alkyl,lower alkoxy, lower alkanoylamino, cyano, or lower alkoxycarbonyl; and mis 1 or 2; and C' is an aniline, tetrahydroquinoline, or benzomorpholinetype coupler selected from those of the formulae ##STR74## wherein R¹⁵and R¹⁶ are each selected from hydrogen, fluorine, chlorine, bromine,lower alkyl, cycloalkyl, lower alkoxy, trifluoromethyl, phenoxy, loweralkylthio, arylthio, and radicals having the formula --NH--X'--R²³ inwhich X' is --CO--, --COO--, or --SO₂ --, and R²³ is selected from loweralkyl and lower alkyl substituted with halogen, hydroxy, phenoxy, aryl,cyano, cycloalkyl, lower alkylsulfonyl, lower alkylthio, loweralkanoyloxy, and lower alkoxy, and when X' is --CO--, R²³ is furtherselected from hydrogen, amino, lower alkylamino, lower alkylcarbamoyl,lower dialkylamino, arylamino, aryl, furfuryl and furyl; R¹⁷ and R¹⁸ areselected from hydrogen; cycloalkyl; cycloalkyl substituted with one ortwo groups selected from lower alkyl, --OH, lower alkoxy, halogen andhydroxy substituted lower alkyl; phenyl or phenyl substituted with loweralkyl, lower alkoxy, halogen, lower alkanoylamino, cyano or loweralkoxycarbonyl; straight or branched lower alkenyl; straight or branchedalkyl of 1-8 carbons and such alkyl substituted with the following:hydroxy; halogen; cyano; amino; succinimido; glutarimido; phthalimido;2-pyrrolidono; cyclohexyl; phenyl or phenyl substituted with loweralkyl, lower alkoxy, halogen, lower alkanoylamino, cyano or loweralkoxycarbonyl; lower alkanoyloxy; lower alkanoylamino; sulfamoyl; loweralkylsulfamoyl; vinylsulfonyl; acrylamido; phthalimidinyl;benzoylsulfonicimidyl; lower alkylsulfonamido; phenylsulfonamido; loweralkoxycarbonylamino; lower alkylcarbamoyloxy; lower alkoxycarbonyl;lower alkoxycarbonyloxy; lower alkenylcarbonylamino; ##STR75## Wherein Yis --NH--, ##STR76## --O--, --S--, or --CH₂ O--; --S--R²⁴ wherein R²⁴ islower alkyl, phenyl, phenyl substituted with halogen, lower alkyl, loweralkoxy, lower alkanoylamino, cyano, or lower alkoxycarbonyl, pyridyl,pyrimidinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, triazolyl, or##STR77## --SO₂ R²³ ; --COOR²³ ; --OX'R²³ ; --NH--X'--R²³ ; --X'--R²³ ;--OCO--R²³ ; --CONR²⁵ R²⁵ ; --SO₂ NR²⁵ R²⁵ ; wherein R²³ and X' are asdefined above and each R²⁵ is selected from H and R²³ ; lower alkoxy;lower alkoxy substituted with hydroxy, cyano, lower alkanoyloxy, orlower alkoxy; phenoxy; phenoxy substituted with one or more of loweralkyl, lower alkoxy or halogen; and R¹⁷ and R¹⁸ combined in the anilinecouplers to form with the nitrogen atom a ring containingpentamethylene, ethyleneoxyethylene or ethylenesulfonylethylene groups;R¹⁹, R²⁰, R²¹ and R²² are each selected from hydrogen and lower alkyl.2. An azo compound according to claim 1 wherein the coupler moieties C'have the formulae ##STR78## wherein R¹⁵ is lower alkyl, lower alkoxy,lower alkanoylamino, or lower alkoxycarbonylamino;R¹⁶ is hydrogen, loweralkyl, or lower alkoxy; R¹⁷ and R¹⁸ are the same or different andselected from hydrogen; lower alkyl; and lower alkyl substituted with1-3 of hydroxy, lower alkoxy, lower alkoxyalkoxy, hydroxy lower alkoxy,carbamoyl, lower alkylcarbamoyl, amino, lower alkanoylamino, sulfamoyl,lower alkylsulfamoyl, phenyl, cyclohexyl, 2-pyrrolidono, phthalimido,succinimido, cyano, phenoxy, lower alkylsulfonyl, phthalimidinyl,benzoylsulfonicimidyl, triazolylthio, lower alkylsulfonamido, --SO₂ NH₂,--SO₂ NH lower alkyl, phenylsulfonamido, lower alkoxycarbonylamino,lower alkylcarbamoyloxy, lower alkoxycarbonyl, lower alkanoyloxy, loweralkoxycarbonyloxy, ##STR79## R¹⁹ and R²¹ are each hydrogen or loweralkyl.
 3. The azo compound according to claim 1 having the formula##STR80##
 4. The azo compound according to claim 1 having the formula##STR81##
 5. The azo compound according to claim 1 having the formula##STR82##
 6. The azo compound according to claim 1 having the formula##STR83##
 7. The azo compound according to claim 1 having the formula##STR84##